New thiazole derivatives of 1.4 naphthoquinone



Patented Aug. 27, 1929.

UNITED STATES WILHELM HERZBERG, or BERLIN, AND GERHARD HOPPE, F BERLIN-in ow, GERMANY, ASSIGNOBS, BY MESNE ASSIGNMENTS, T0 GENERAL ANILINE worms, INC., on NEW YORK, N;'Y., A CORPORATION OF DELAWARE.

NEW THIAZOLE DERIVATIVES OF 1.4 NAPHTHOQUINONE.

o Drawing. Application filed December 28, 1926, Serial No. 157,607, and in Germany November '18; 1925.

Our invention relates to new thiazole derivatives of 1.4-naphthoquinone, represented by the formlua:

l B being an organic radical. These thiazolev 1 derivatives may be obtained by condensing 2-amino-3-mercapto 1.4-naphthoquinone with an aldehyde, such as acetaldehyde', glyoxal, benzaldehyde, naphthaldehyde, terephthalaldehyde. The yellow thiazole derivatives are soluble in concentrated sulfuric acid with a yellowish color. They yield with sodium hydrosulfite in the presence of a strong alkaline agent a vat, from which cotton is dyed yellow tints.

The condensation of 2-amino-3-mercapto- 1.4-naphthoquinone with aldehydes occurs very smoothly, most simply in aqueous suspension. There is first obtained an intermediate' product which evidently passes extraordinarily easily into a thiazole by action of atmospheric oxygen. These intermediate products may be used directly in dyeing as they are converted into the vat of the finished 3 dye by treatment with-alkali and hydrosul- The following example, the parts being by weight, illustrates the invention without lim- .iting it:

1y warming'22 parts of 2-amino-3-chloro-1A- naphthoquinone with 25 parts of crystallized vsodium sulfide in 120 parts of water, 12 parts" brown amorphous matter which first separates is thus converted into ayellow crystal- To the blue solution .of 2-amino'-.3-mer-, capto-l.4-naphthoquinone, obtained by gent line body. This product, recrystallized from glacial acetic acid, forms greenish yellow needles which decompose at 225 to 230 C. It corresponds probably to the formula:

When gentlywarmed withdilute sodium hydroxide solution it dissolves in part to a blue-red solution; by adding sodium hydrosulfite the solution is complete. From this solution oxidation with air precipitates the dye. The product first obtained is advantageously further worked up by dissolving it in about 50 parts ofwater, 1 part of sodium hydroxide solution of 35 B. and 1 part of sodium hydrosulfite and thenintroducing air. The greenish yellow powder thus ob.

--Th e conipound derived from Q-amino- 3-mercaptoJA-Iiaphthoquinone and terephthalaldehyde is soluble in concentrated sulfuric acid with a yellowish color and yields with sodium hydrosulfite and sodium hydroxide a vat from which cotton is dyed yellow tints and corresponds to the probable formula v:

\Vhat we claim is: '1. The new thiainole derivatives of 1.4-

:naphthoquinone, represented by the formula B being an organic radical, soluble in concentrated sulfuric acid with a yellowish color and yielding with sodium hydrosulfite. and

sodium hydroxide a vat from which cotton is dyed yellow tints.

2. The new thiazole compounds derived from 2 amino 3 mercapto 1A naphthoqu-inone and an aldehyde, soluble in concentrated sulfuric acid with a yellowish color and yielding with sodium hydrosulfite and sodium hydroxide a Vat from which cotton is dyed yel-' low tints.

3. The new thiazole compounds derived from 2 amino 3 mercapto lA-naphthoquinone and an aromatic aldehyde, soluble in concentrated sulfuric acid with a yellowish colorand yielding with sodium hydrosulfite and sodium hydroxide a vat from which cotton is dyed yellow tints, the new compounds containing inv their'molecule twice the radical 5. The new thiazole compound derived from 2 amino-3-mercapto 1.4 naphthoquinone and terephthalaldehyde, soluble in concentrated sulfuric acid with a yellowish color and yielding with sodium hydrosulfite and sodium hydroxide a vat from which cotton is dyed yellow tints, thenewcompound corresponding to the formula:

Intestimony whereof we afliir our signatures.

' jWILHELM HERZBERG.

GERHARD HOPPE. 

